Vat dyestuff printing paste



Patented Dec. 3, 1935 UNITED- STATES v PATENT This inventio pastes fortexti characteristics the print. th

of this invention proceeds.

' We have found that vat dyestufls which are normally but poorly adaptedfor printing in view of the weak prints they produce may have theirtinctorial strength considerably increased by incorporating into theprinting paste a vat dyestui'i of substantially similar color butpossessing relatively increased solubility in the vat. The

,latter will hereinafter be referred to as the assistant vat dyestufl.By relatively increased solu-' bility, we are referring to thesohibility of the assistant vat dyestuif as compared to the solubilityof the principal vat dyestuii itself which is used to produce thedesired color. By the vat, we are referring to the standard alkalinehydrosulflte ,vat used for reducing and dissolving vat dyestuffs.Although the vat itself is not used in printing proces to act as an aspaste.

The above effect may be illustrated by considering the dyestuff,

-. VAT nmsrorr rnm'rme PASTE Philip H. Stott, Penns Grove, N. J., andEarl Edson Beard, South Milwaukee, Wis., assignors to E. I. du Pont deNemours & Company, Wilmington, Del., a corporation of Delaware NoDrawing. Application March 8, 1933,

Serial No. 660,076 r 8 Claims. (01. 8-6) 11 relates to vat dyestuffprinting le fabric. It is an object of this or even higher.

of the paste, and brightness of er and further important objects willappear as the description OFFICE.

The proportion of the assistant to principal dyestufi may vary withinwide limits. It may be as low as 1:10 or as high as 1:1 by weight, Thebeneficial effect generally increases with increased proportions. Asalready noted, this beneficial effect may be observed on the tinctorialstrength of the principal dyestuif, the brightness of the resulting.print, and the ageing qualities. The ageing period required forbringing out the full efi'ect of the color is gen- 0 'erallyconsiderably shortened.

The above efiects are particularly useful in the case of the yellow toorange dyestuffs of. the algol series, since a good printing yellow ofthe 15 vat dyestufi series has been wanting for some time. Theassistants for colors of this type are acylamino-anthraquinones. In thefollowing table is shown a number of dyestuifs and combinations of theyellow to orange series which have been considerably improved by theaddition of an assistant of the acylamino-anthraquinone Color ses, thesolubility of a given vat Assistant qumone sistant in a vat dyestufiprinting 3. o. 1 4.- l-benzoylamino-5-(l,9-antl1ra1so- 1,5idibenz y1 dii thiazole-2-carbonyD-amino-an- Parts 1. Dibenzoyl 1,5 diamino anthra 90Parts Dibenzoyl 1,8 diamino anthraquinthraquinone. This compound, whenused by it- 5. sfifiitififiifisiiryrisneanz; 80 d0. 1 self in the usualprinting pastes, produces ver'y wthraquinwq"; 30 weak yellow prints. If,however,- admixed with 6, Do.1 so }1-benzoi5iii'fi$5i 1,8 dibenzoyldiamino anthraquinone, which I 1 thraqmnofle 0 possesses substantiallythe same color as the 1,5- 7 iig g 1 (m1 30 isomer, but is considerablymore soluble in the f f i fj 30 vat, the resulting prints possessincreased Do.4 m 40 n h, brilliance. and improved ageing quali-,';,?,,;';1 5, 1 so ties. The remarkable point is that1,8-dibenzoyldigiazole 30 o. 5 30 diamino-anthraquinone itselfconstitutes but a 9 Pmnthmne 10 m1 30 very poor printing color. Themixture thus prof ifif gzgig f'ffffffififfff: 30 duces effects whichcould not be predicted from i he yI zjifis annim uinonethe Pmperties 0fits individual components 10. $31 ,332, :1133;113:1131:: i3 do.l 30

For best results, the assistant should be in fine- Di pligpyl ,1,6, t q30 ly divided form. This form can best be obfj :2i 555:;55gf tained bydissolving the assistant in concentratn g g fii l-g I an 1 30 edsulfuric acid, drowning the solution in water,Diphenyl-2,1,6,5-anthraquin0ne- 50 filtering and washing. The resultingpaste may dithiazole 80 D1anisyl-1,8-diaminobe mixed with the aqueouspaste of the prin- 12. Do.i1 g anthmquinomun 30 cipal dyestuii', oritmay be incorporated into the thickening-and-retiucing paste eitherprior to or after the introd uction of. the main dyestuflf paste.

Instead of the-particular assistants mentioned above, any otheracylamino-anthraquinone may be used whose solubility in the vat isgreater than that of the principal dyestufi employed. Examples of suchadditional assistants are:

aor fi-acetylamino-anthraquinone; aor 8- benzoyl-amino-anthraquinone;1,4-dibenzoyl-diamino anthraquinone; l-benzoyl-aminoior 8-halogen-anthraquinone; l-benzoylaminoior 8- amino-anthraquinone;l-benzoylamino-ior 8- hydroxy-anthraquinone; alkyl ethers of the latter;l-benzoylamino-anthraquinone-6-carboxyl ic acid;hydroxy-benzoylamino-anthraquinone; the imide of1,9-anthrathiazol-Z-carboxylic acid and aor ,e-amino-anthraquinone; theimide of a 1-aroylamido-anthraquinone B-carboxylic acid and aorp-amino-anthraquinone; the di-imide obtained from two moles of al-aroylamido-anthraquinone-G-carboxylic acid and one mole of1,8-diamino-anthraquinone (the latter is particularly advantageous wherethe corresponding 1,5- di-imide is used as the principal dyestufi) thedi-imide from two moles of anthraquinone-2- carboxylic acid and1,8-diamino-anthraquinone; the imide of anthraquinone-Z-cz'arboxylicacid and ccor p-amino-anthraquinone; and many others.

Without limiting the invention the following examples are given toillustrate the process of preparing and using our improved printingpastes.

Example 1. Preparation of dyestufl paste containing both the principalcolor and the assistant 1 part of crudedibenzoyl-l,8-diamino-anthraquinone in powder form is suspended in 12parts of sulfuric acid, maintained at 5 C., and stirred until completelydissolved. The solution is then poured into 250 parts of ice water,filtered and washed acid-free. The filter cake is suspended in 40 partsof water, the mass is warmed up to 80-85 C., and 5 to 10 parts. of a 10%alkaline hypochlorite solution are added, and the mass is maintained atthis temperature for 2-4 hours. It is then filtered and washed free ofalkali. Water is then added to temper the paste to the desiredconsistency, which is usually made to correspond to about 15 to 20% ofsolid material by weight. .015- parts of a 30% leucanol solution, or asuitable quantity of any other wetting agent is then added, and thepaste is milled to the desired degree of fineness.

2 parts of dibenzoyl-1,5-diamino-anthra- I quinone are made into a pasteby substantially the same procedure as above, using correspondinglyincreased proportions of the various materials. The two pastes are mixedtogether and. subjected to joint milling untilthoroughly uniform.

Example I 2 rest of theprocedure is then substantially like."

in Example 1, except that correspondingly increased proportions of thevarious materials are used throughout. In'this process the intermixingof the principal dyestuff and assistant occurs during the step ofdissolving in sulfuric acid, and

the result is a very uniform paste excellently adapted for printingpurposes.

Preparation of the printing past and process of. printing 7 Example 3.

' Parts 5 Wheat starch (dry) 55 British gum 6% gum tragacanth solution55 Water 275 10 Potassium carbonate Sodium formaldehyde sulfoxylate- 160Glycerine 100 Total 1000 15 A printing paste is now prepared by mixingtogether thoroughly 80 parts of the above thickening-and-reducing pasteand 20 parts of the dyestufi paste prepared according to either ofExamples land 2. Cotton fabric or cloth is then 20 printed with thispaste in the usual manner, and dried. It is then steamed in a rapid agerfor 2 to 8 minutes, at a temperature of 101-102 C. The print is thenoxidized in a dilute sodiumbichromate solution or in cold running water,25 after which it is soaped, rinsed and dried.

The print so prepared by the use 01' a mixture 0tdibenzoyl-1,5-diamino-anthraquinone and dinbenzoyl-1,8-diaminoanthraquinone is considerably stronger and brighter,after 8 minutes age- 30 ing, than prints prepared by the use of eithercomponent alone under similar conditions.

It will be understood that the use of our novel assistants as aboveillustrated does not exclude the use of other printing assistants ordispersing 35 agents. On the contrary, it is-advantageous to use suchadditional assistants and dispersing agents as are known to the art, forinstance, the various iso-propyl-naphthalene sulfonic acids, the varioussulfonic acids of the abietene family; 40 diethylene glycol;polyhydroxyl-alkyl-amlnes, and the like.

In general, it should be understood that numerous variations andmodifications may be introduced in our preferred procedure above setforth, without departing from the spirit of this invention.

We claim:

1. The process of improving the printing qualities of a vat dyestufl' oithe algol-series, which comprises incorporating into the printing pastecontaining the same an acylamino-anthraquinone characterized by highsolubility in the alkaline hydrosulfite vat.

2. The process of improving the printing quallties 01' a.1,5-diaroyl-diamino-anthraquinone, which comprises incorporating into aprinting paste containing said compound a1,8-diaroyldiamino-anthraquinone.

3. A printing paste comprising as principal color ayellow to orange vatdyestuii of the anthraquinone series, and as assistant anasylamino-anthraquinone having a greater solubility in the alkalinehydrosulfite vat than the anthraquinone dyestufl with which it is used..5 4dr printlng paste comprising as principal color a-vat dye'stufi .of.the algol series, and as assistant an acylamino-anthraquinonecharacterized by high solubility in the alkalinehydrosulfite vat. v 705. A printing paste. comprising a. 1,5-di'aroyldiamino-anthraquinone asprincipal color, anda I 1,8-diaroyl-diamino-anthraquinone as t, theratio of the latter to the former being between 1/10 and 1. r

6. A printing paste comprising substantially 30 parts ofdibenzoyh1,5-diamino-anthraquinone, 30 parts ofdibenzoyl-L8-diamino-anthraquinone, 10 parts of pyranthrone, and 30parts of diphenyl- 2,1,6,5-snthraquinone-dithiazole.

7. A printing paste comprising substantially 30 parts of 1benzoylamino-5-(1,9-anthraisothiazole-2-carbonyl) -amino-a.nthraquinone,30 parts of dibenzoyl-LB-diamino-anthraquinone, 10 parts of pyranthroneand 30 parts of diphenyl-2',1,6,5- anthraquinone-dithiazole.

8. A printing'paste comprising substantially 30 parts ofdiphenyl-2,1,7,8-anthraqulnone-dithiazole, 30 parts'ofdibenzoyl-L8-diamino-anthraquinone, 10 parts of pyranthrone and 30 partsof diphenyl-2,1,6,5-a.nthraquinone-dithiazole.

PHILIP H. STOTT. EARL EDSON BEARD.

